TW201107879A - Actinic ray-sensitive or radiation-sensitive resin composition, resist film, and pattern-forming method using the same - Google Patents

Abstract

Provided is an actinic ray-sensitive or radiation-sensitive resin composition, a resist film formed with the composition, and a pattern-forming method using the same. The actinic ray-sensitive or radiation-sensitive resin composition includes (P) a resin that contains the following repeating units (A), (B) and (C); and a solvent having a boiling temperature of 150 DEG C or less, (A) a repeating unit containing a group capable of decomposing and forming an acid upon irradiation with an actinic ray or radiation, (B) a repeating unit containing a group capable of decomposing and forming a carboxylic acid by the action of an acid, and (C) a repeating unit containing a carbon-carbon unsaturated bond.

Description

201107879 VI. Description of the Invention: [Technical Field] The present invention relates to a sensitized ray or a radiation sensation which is preferably used in ultramicro lithography (such as manufacturing of super LSI and high-capacity microchips and other optical manufacturing processes) A resin composition, a photoresist film formed from the composition, and a pattern forming method using the same. More specifically, the present invention relates to a positive-type photoresist composition for electron beam, X-ray or EUV light ray, a pattern forming method using the same, and a resin for a positive type resist composition. [Prior Art] A lithography precision program of a photoresist composition is conventionally performed in a process of a semiconductor device such as 1C and LSI. In recent years, integration with hoarding circuits has required the formation of ultra-precision patterns in sub-micron regions and quarter-micron regions. In this case, the exposure wavelength also shows a tendency to become shorter, such as from the g-line to the i-line, and further to the KrF excimer laser light. In addition to KrF excimer laser light, the development of lithography using electron beam, X-ray or EUV ray is now being carried out. In particular, electron beam lithography is positioned as a next-generation or next-generation patterning technique, and requires high sensitivity and 髙 resolution positive photoresist. Increasing sensitivity is a particularly important issue in order to reduce wafer processing time. However, the higher sensitivity of the positive-type photoresist for electron beam is not only accompanied by a decrease in resolution but also a deterioration in line width, and thus there is a strong need to develop a photoresist which satisfies these characteristics at the same time. Here, the thickness of the line edge indicates that the edge at the interface between the photoresist pattern and the substrate irregularly fluctuates in the direction of the vertical line (attributed to the photoresist feature of 201107879), and the edge is not seen when viewing the pattern directly above. Uniformity This unevenness shifts in the etching process using this photoresist as a mask and degrades electrical characteristics to reduce yield. Especially in ultra-precision areas of 0.25 micron or less, the thickness of the line edge is an extremely important problem to be improved.髙 Sensitivity, high resolution, good pattern form, and good line edge roughness are important, and how to satisfy these properties at the same time is very important. It is also important to satisfy high sensitivity, high resolution, good pattern form, and good line edge roughness in the use of X-ray and EUV ray lithography, and the solution is necessary. It is reviewed that a resin having a photoacid generator in the main chain or side chain of the polymer is used as a means to solve these problems (JP-A-9-325497 (the term "JP-A" is used herein to mean "unexamined disclosure". Japanese Patent Application No.), JP-A-10-221852, JP-A-2006-178317, JP-A-2007-197718, WO 2006/121096, US 2006/121390, US 2007/117043 Patent, JP-A-2008-133448, and Proc. of SPIE, 692 3, 6 923 1 2,200 8 ) » However, in the review of JP-A-9-3 2 5 49 7 Since the composition is a mixing system of a resin having a photoacid generator and a dissolution inhibiting compound which can increase solubility in an alkali developer due to acid decomposition, it is difficult to obtain a good pattern form and a line edge roughness (attributable to The heterogeneous nature of these materials). On the other hand, JP-A-10-221852, JP-A-2006-178317, JP-A-2007-197718, WO2006/121096, and US200 6/121390 are disclosed in the same molecule. A tree 201107879 grease having a photoacid generating group and a base which is decomposed by the action of an acid and which increases the solubility in an alkali developer is not considered to be sufficiently sensitive to electron beam, X-ray or EUV rays. Further, US 2007/117043, and Proc_ of SPIE, vol. 6923, 692, 312, 2008 disclose a terpolymer comprising hydroxystyrene, an adamantyl containing acrylate, and an acrylate containing a photoacid generator. JP-A-2 00 8 - 1 3 3 448 discloses a high-energy ray or sensible photoresist which contains a repeating unit which produces sulfonic acid at the fluorine-containing terminal of the side chain to improve high resolution Resin with fine/dense deviation and exposure limit. On the other hand, in electron beam, X-ray or EUV ray lithography, the volatile components from the photoresist film are exposed to very expensive exposure equipment due to degassing. However, if a large amount of solvent having a high boiling temperature is used as the photoresist solvent, the solvent is still in the film and causes degassing. There is therefore a need to develop a resin component which is soluble and coated as much as possible in a multi-purpose solvent having a low boiling temperature. · Therefore, the current situation is that electron beam, X-ray or EUV ray lithography cannot fully satisfy high sensitivity, high resolution, good pattern form, and good line edge roughness by the combination of currently known technologies. And degassing performance. In addition, the precision processing of the photoresist composition is not only directly used for the manufacture of integrated circuits, but also used in the manufacture of mold structures (referred to as imprinting) in recent years (for example, refer to JP-A-2004-158287, JP-A-2008- 162101, and Fundamentals, Technical Development and Development of Applications of Nano-Imprinting - Techniques on

Substrates And The Latest Technical Development of 201107879

Nano-Imprinting -, compiled by Yoshihiko Hirai, published by Frontier Publishing Company (June 2006)). Therefore, even if X-ray, soft X-ray or electron beam is used as the exposure light source, it is important to satisfy high sensitivity, high resolution, good pattern form, good line edge roughness, and degassing performance. And it is necessary to solve these problems. SUMMARY OF THE INVENTION It is an object of the present invention to provide an ultra-precision region, particularly in electron beam, X-ray or EUV ray lithography, while satisfying high sensitivity, high resolution, good pattern form, and good A wire edge roughness, a sensitized ray or a radiation sensitive resin composition which is reduced in degassing, and another purpose is to provide a pattern forming method using the same. It has been found that the above objectives are achieved by the following composition. &lt;1&gt; A sensitized ray or radiation sensitive resin composition comprising: (P) a resin comprising the following repeating units (A), (B) and (C); and a boiling temperature of 150 ° a solvent of C or lower, (A) - a repeating unit containing a group which decomposes and forms an acid upon irradiation with actinic rays or radiation, (B) a substance which decomposes due to an action of an acid and forms a carboxylic acid a repeating unit of a group, and (C) a repeating unit containing a carbon-carbon unsaturated bond. &lt;2&gt; The photosensitive ray or radiation sensitive resin composition according to <1>, wherein the repeating unit (B) is a repeating unit represented by the following formula (I), and 201107879

R〇i, 1^2 and rQ3 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a dentate atom, a cyano group, or an alkoxycarbonyl group, and R〇3 may represent an alkylene group and bond L or Q. Forming a 5- or 6-membered ring; L represents a single bond or a divalent bond, provided that the L-bond R()3 forms a 5- or 6-membered ring to represent a trivalent bond;

Ri represents an alkyl group; each R2 and R3 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. & R2 and R3 may be bonded to each other to form a ring, provided that R2 and R3 are different when hydrogen is not present. An atom; and Q represents a group containing a carbon-carbon unsaturated bond. &lt;3&gt; The photosensitive ray or radiation sensitive resin composition according to &lt;1&gt;, wherein the composition of the repeating unit (Β) and the repeating unit (c) in the resin (Ρ) is (mole) The relationship of the repeating unit (B) S repeating unit (c) is satisfied. The photosensitive ray or radiation-sensitive resin composition of any one of <1> to <3>, wherein the resin (P) further contains (D)-type having an alkali-developing agent The repeating unit which acts to decompose and increases the rate of dissolution in the alkali developer, and its line 201107879 is represented by the following formula (All):

among them

Rb〇 represents no hydrogen atom, halogen atom or a hospital base;

Ab represents a single bond, an alkylene group, a divalent linkage having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether bond 'ester bond, a carbonyl group, or a combination thereof; and V represents a base The action of the developer can decompose and increase the basis of the dissolution rate in the alkali developer. The photosensitive ray or radiation-sensitive resin composition according to any one of <2> to <4>, wherein Q in the formula (Π) is an aromatic ring-containing group. &lt;6&gt; The photosensitive ray or radiation sensitive resin composition according to <5>, wherein Q in the formula (II) is a benzene ring-containing group. The photosensitive ray or radiation-sensitive resin composition of any one of <1> to <6>, wherein the resin (P) contains a repeating unit derived from hydroxystyrene or a derivative thereof as a repeat Unit (C). The photosensitive ray or radiation-sensitive resin composition of any one of <1> to <7>, wherein the repeating unit (A) has a kind of resin in the case of irradiation with actinic rays or radiation 201107879 The sensitizing ray or radiation-sensitive resin composition of any one of <1> to <8>, wherein the boiling temperature is 150 ° C or lower. The solvent contains an amount of 65% by mass or more based on the total amount of the solvent. The photosensitive ray or radiation sensitive resin composition according to any one of <1> to <9>, wherein the boiling temperature is 15 (TC or lower of the solvent system based on the total amount of the solvent) The photosensitive ray or radiation-sensitive resin composition of any one of &lt; 1 &gt; to &lt; 1 0&gt; wherein the boiling temperature is 1 50. The solvent of ° C or lower contains an amount of 90% by mass or more based on the total amount of the solvent. &lt; 1 2 &gt;&lt; 1 &gt; to &lt; 1 1 &gt; a radiation or radiation sensitive resin composition in which the resin (P) consists only of the repeating units (A) to (C) or only the repeating units (A) to (D), and all of the repeating units (C) are of the following formula (丨卜: ^ indicates the weight

Wherein Q represents a group containing a carbon-carbon unsaturated bond. &lt;13&gt; The photosensitive ray or radiation sensitive resin composition according to any one of <1> to <12&gt;, wherein the proportion of the repeating unit having a ring structure in the main chain of -10 201107879 in the resin (P) It is 3 % Mo % or less. The photosensitive ray or radiation sensitive resin composition according to any one of the above-mentioned, wherein the resin (P) does not contain a repeating unit having a ring structure in the main chain. The photosensitive ray or radiation sensitive resin composition according to any one of <1> to <14>, wherein the resin (P) has a weight average molecular weight in the range of 1,000 to 1,000,000. The photosensitive ray or radiation sensitive resin composition according to any one of <1> to <15>, further comprising: a basic compound. The photosensitive ray or radiation-sensitive tree fat composition according to any one of <1> to <16>, which is exposed by electron beam, X-ray or EUV radiation. &lt;18&gt; A photoresist film formed of a photosensitive ray or a radiation absorbing resin composition as described in any one of &lt;1&gt; to &lt;17&gt;. &lt;19&gt; A pattern forming method comprising: exposing and developing the photoresist film of &lt;18&gt;. [Embodiment] The present invention will be described in detail below. Incidentally, when a radical (atomic group) is described in the specification of the present invention, the description of the unsubstituted or unsubstituted is not intended to include a substituent-free group and a substituent-containing group. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). -11-201107879 The "actinic ray" or "radiation" of the present invention means, for example, a far-ultraviolet light, an extreme ultraviolet ray, an X-ray, an electron beam or the like represented by a bright line spectrum of a mercury lamp and an excimer laser. Further, "light" in the present invention means actinic rays or radiation. In addition, the term "exposure" in this specification includes not only the use of far-ultraviolet light, X-ray and EUV radiation, which is represented by a laser and excimer laser, but also imaging by microparticle rays (such as electron beam, ion beam, etc.) unless otherwise There are instructions. The sensitized ray or radiation sensitive resin composition of the present invention contains (P) a resin containing repeating units (A), (B) and (C), and a boiling temperature of 15 (TC or lower). Solvent: (A) a repeating unit containing a group which decomposes and forms an acid upon irradiation with actinic rays or radiation, and (B) a repeating unit containing a group which decomposes due to the action of an acid and forms a carboxylic acid. And (C) a repeating unit containing a carbon-carbon unsaturated bond. The repeating unit (A) includes a group which is decomposed and forms an acid upon irradiation with actinic rays or radiation, and also contains a carbon-carbon unsaturated bond. a repeating unit based on the repeating unit (A), any repeating unit may be used as long as it is a repeating unit which decomposes and forms an acid upon irradiation with actinic rays or radiation, but the repeating unit (A) preferably has a a repeating unit of a structure capable of generating an acid anion in a side chain of a resin when irradiated with actinic rays or radiation. The repeating unit (A) is preferably, for example, any one of the following formulas (ΠΙ), (IV), and (V)-12 - 201107879 Representation of repeating unit

(m)

In the formulae (III) to (V), each of RQ4, r〇5, and rQ7 to rD9 independently represents a gas atom, a hospital group, a ring-based group, a halogen atom, a fluorenyl group, or an alkoxy group. R〇6 represents a hydrogen atom, a cyano group, a fluorenyl group, -CO-〇r25, -CO-N(R26)(R27). R26 and r27 may bond to a nitrogen atom to form a ring. Each X!, X2 and X3 independently represents a single bond, an extended aryl group, an alkylene group, a cycloalkyl group, -0-, -S〇2-, -CO-, -N(R33)-, or a combination thereof. A divalent bond group derived from two or more groups. R2 5 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or an aralkyl group. Each of Κ·26, R_27 and Κ·33 independently represents a hydrogen atom, a hospital group, a ring-based group, an alkenyl group, an aryl group or an aralkyl group. Α denotes a moiety which decomposes and produces acid upon irradiation with actinic rays or radiation. With respect to the alkyl group represented by R〇4, R〇5' and 11.7 to R〇9 in the formulae (III) to (V), it is preferably exemplified by substituted or not having 20 or less carbon atoms. a substituted alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, and more preferably exemplified An alkyl group of 8 or fewer carbon atoms. As the cycloalkyl group, a monocyclic or polycyclic cycloalkyl group is exemplified. Preferably, it is -13.201107879 a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and more preferably a fluorine atom are exemplified. As the alkyl group contained in the alkoxycarbonyl group, it is preferably the same alkyl group as RG4, R05, and R〇7 to R〇9. As the alkyl group represented by R25 to R27 and r33, a substituted or unsubstituted alkyl group having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, is preferably exemplified. The group, the second butyl group, the hexyl group, the 2-ethylhexyl group, the octyl group, and the dodecyl group, and more preferably an alkyl group having 8 or less carbon atoms. As the cycloalkyl group, a monocyclic or polycyclic cycloalkyl group is exemplified. Preferably, it is a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. As the alkenyl group, a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms such as a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a ring is preferably exemplified. Hexenyl. As the aryl group, it is preferably a substituted or unsubstituted monocyclic or polycyclic aromatic group having 6 to 14 carbon atoms, and particularly exemplified by a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group. , with naphthyl. The aryl groups may be bonded to each other to form a polycyclic ring 9 to the aralkyl group, which is exemplified by a substituted or unsubstituted aralkyl group having 7 to 15 carbon atoms, such as benzamidine, phenethyl and cumyl. As for the ring formed by bonding R26 and R:w with a nitrogen atom, it is preferably a -14-.201107879 5 - to 8-membered ring, and particularly exemplified by pyridin D, piperazine and pipe well. The aryl group represented by each of Xi, X2 and X3 is preferably a substituted or unsubstituted extended aryl group having 6 to 14 carbon atoms, and particularly exemplified is a phenyl group, a tolyl group and an anthranyl group. The alkyl group may be a straight chain or a branched chain. The number of carbon atoms of the linear alkyl group is preferably from 2 to 20, more preferably from 3 to 18, and still more preferably from 4 to 16. The number of carbon atoms of the branched alkyl group is preferably from 4 to 20, and more preferably from 5 to 18. As the designated examples, examples thereof include an ethyl group, a propyl group, a butyl group, a hexyl group, and a octyl group. The cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 5 to 8 carbon atoms, and examples thereof are a cyclopentyl group and a cyclohexylene group. Preferred examples of the substituent which each of the groups in the formulae (ΠΙ) to (V) may have include a hydroxyl group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, a decylamino group, and a sulfonate. Alkyl, alkoxy (exemplified by methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy) exemplified in guanamine, RG4 to RG9, R25 to R27, and R33 Alkoxycarbonyl (eg methoxycarbonyl and ethoxycarbonyl), fluorenyl (eg, formazan, ethenyl and benzhydryl), decyloxy (eg ethoxylated with butyl) Alkoxy), and a carboxyl group. The number of substituents is preferably 8 or less. A represents a moiety which decomposes and generates an acid upon irradiation with actinic rays or radiation, and particularly exemplifies a photoinitiator for cationic photopolymerization, a photoinitiator for radical photopolymerization, a photodecolorizer for dye, and light. A color changing agent, and a structural part of a known compound which is used for the action of light by a micro-resistance or the like to generate an acid. ' -15- 201107879 As for the structural part which can decompose and generate an acid anion when irradiated with actinic rays or radiation, examples of the example are gun structure parts such as diazonium salt, ammonium salt, scale salt, iodized salt, barium salt, selenium. Salt, and barium salt. A is more preferably an ionic moiety containing a phosphonium salt or an iodide salt. More specifically, A which can generate an anion on the side chain of the resin when irradiated with actinic rays or radiation is preferably a group represented by the following formula (ZI) or (ZII). In the formula, a straight line extending to the left by Z' is a bonding hand extending toward the main chain of the repeating unit (A). —Ζθ|~R202 R2〇4_,_&quot;R205

Zi R203 ZII In the formula (ZI), each of r2Q1, R2Q2 and r2〇3 independently represents an organic group. The number of carbon atoms represented by each of r2D1, r2Q2 and R2G3 is usually from 1 to 30, and preferably 1 to 20. Further, two of R2G1, R2Q2 and R2Q3 may be bonded to each other to form a ring, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond, or a carbonyl group. As for the bond R2 (the base formed by the two of M, R2Q2 and R2Q3, an alkyl group (for example, a butyl group and a pentyl group) can be exemplified. Z' represents a decomposition and generation when irradiated with actinic rays or radiation. An acid anion, and preferably a non-nucleophilic anion. As far as the non-nucleophilic anion is concerned, examples thereof include a sulfonic acid anion, a carboxylic acid anion, a phosphate anion, a sulfonyl quinone imine anion, and an anthracene. a quinone imine anion, and a sulfhydryl methine anion. -16- 201107879 Non-nucleophilic anion is a very low ability to cause nucleophilic reactions, and may be due to intramolecular nucleophilicity. The reaction inhibits the anion which is decomposed by aging. Therefore, the presence of the non-nucleophilic anion improves the aging stability of the resin and improves the aging stability of the photoresist. As for the organic group represented by each R 2 (M, R 2 Q 2 and R 203, an example thereof a base, an alkyl group, a cycloalkyl group, a cycloalkenyl group, and a fluorenyl group. In the cycloalkyl group and the cycloalkenyl group, at least one ring-forming carbon atom may be a carbonyl carbon. Preferably, R2 (M, R2Q2 and At least one of R2G3 is an aryl group, and more The aryl group represented by R2Q1, R2Q2 and R2()3 is preferably a phenyl group and a naphthyl group, and more preferably a phenyl group. It is represented by each of R2Q1, R2Q2 and R2Q3. An alkyl group, a cycloalkyl group and a cycloalkenyl group each having a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), having 3 to 10 a cycloalkyl group of a carbon atom (e.g., a cyclopentyl group, a cyclohexyl group, a norbornyl group), and a cycloalkenyl group having 3 to 1 unit carbon atoms (e.g., a cyclopentadienyl group, a cyclohexenyl group) The organic group represented by each of R2Q1, R2〇2 and R2Q3 (e.g., aryl, alkyl, cycloalkyl, cycloalkenyl, and fluorenyl) may further have a substituent. Thus, the substituent is exemplified by a nitro group and a halogen. An atom (e.g., a fluorine atom), a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkyl group (preferably having 1 to 15 carbon atoms), an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkane a base (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 2 to 7 carbon atoms), Mercapto-17-201107879 (preferably having 2 to 12 carbon atoms), alkoxyneoxy group (preferably having 2 to 7 carbon atoms), and arylthio group (preferably having 6 to 14) a carbon atom), a hydroxyalkyl group (preferably having 1 to 15 carbon atoms), an alkylcarbonyl group (preferably having 2 to 15 carbon atoms), a cycloalkylcarbonyl group (preferably having 4 to 15 carbons) An atom), an arylcarbonyl group (preferably having 7 to 14 carbon atoms), a cycloalkenyloxy group (preferably having 3 to 15 carbon atoms), and a cycloalkenylalkyl group (preferably having 4 to 20 carbon atoms) a carbon atom), but the substituent is not limited to these groups. In the cycloalkyl group and the cycloalkenyl group which may be a substituent which each group represented by R2G1, R2G2 and R2〇3 has, at least one carbon atom forming a ring It can be a carbonyl carbon. Each of the substituents which each group represented by R2 &lt;n, R2〇2 and R2G3 may further have a substituent, and examples of the substituent may be exemplified as the groups represented by R2 (n, R2〇2 and R2G3) The same substituent which may be exemplified for each substituent, but is preferably an alkyl group and a cycloalkyl group. As for the case where at least one of R2G1, R2G2 and R2G3 is not an aryl group, it may be exemplified as a cationic structure such as JP. -A-2 004-2 3 3 66 Patent No. 1, [0046] and [0047], JP-A-2003-35948, [0040] to [〇〇46], disclosed by US Patent The compound represented by the formula (1-1) to (1-7 0) in the application No. 2003/0224288, and the formula (IA-1) to (IA-54) and the formula (IB) of the US Patent Application No. 2003/0077540 -1) to a compound represented by (IB-24). In the formula (ZII), each R2Q4 and R2G5 independently represents an aryl group, an alkyl group or a cycloalkyl group. These aryl groups, alkyl groups and cycloalkyl groups and descriptions The radical represented by the formula (ZI) -18-201107879 is the same as the aryl group of the R2G1, r2〇2 and r2G3, and the alkyl group and the cycloalkyl group. The aryl group represented by each of 1^04 to 112〇7 may be Miscellaneous An aryl group having a ring structure (having an oxygen atom, a nitrogen atom or a sulfur atom). As the aryl group having a heterocyclic structure, for example, a pyrrole residue (a group formed by removing a hydrogen atom from pyrrole), a furan residue ( a base formed by removing a hydrogen atom from furan), a thiophene residue (a group formed by removing a hydrogen atom from thiophene), a hydrazine residue (a group formed by removing a hydrogen atom from hydrazine), a benzofuran residue a group (a group formed by removing a hydrogen atom from benzofuran), and a benzothiophene residue (a group formed by removing one hydrogen atom from benzothiophene). An aryl group or an alkane represented by each of R2〇4 and R2GS The group and the cycloalkyl group may have a substituent. Thus, the substituent is exemplified as the aryl group represented by R2()1 to R203 in the formula (ZI), and the alkyl group and the cycloalkyl group may have the same group. An acid anion which is decomposed and produced upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion, which is exemplified by the same anion represented by Z. in the formula (ZI). Side chain of resin when irradiated The A which can generate a cation is also preferably a group represented by the following formula (ZCI) or (ZCII). In the formula, a straight line extending from s + and 1+ to the left is an extension toward the main chain of the repeating unit (A). The key of the hand. ^301 Ι.Θ ^ Θ f Μ \ Latch 3. 3 Μ

Rs02 zcn ζα -19- 201107879 In the formula (ZCI) or (ZCII), each of the scales 3()1 and R3〇2 independently represents an organic group. The number of carbon atoms in the organic group represented by each of R3 CM and R3 02 is usually from 1 to 30 and preferably from 1 to 20. Further, R3G1 and R3Q2 may be bonded to each other to form a ring, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond, or a carbonyl group. As the group formed by the bonding R3G1 and R 3 0 2. , an alkyl group (for example, a butyl group, a pentyl group) can be exemplified as the organic group represented by R3Q1 and R3〇2, which can be specifically exemplified as a formula. (ZI) R2 (aryl group, alkyl group and cycloalkyl group of the examples of H to R2Q3. Μ· represents a non-nucleophilic anion, which may, for example, be an sulfonic acid-containing anion compound, a carboxylic acid-containing anion compound, or a phosphoric acid-containing compound An anionic compound, a sulfonium sulfonium iodide anion compound, an anthracene (alkylsulfonyl) quinone imine compound, and a hydrazine-containing (alkylsulfonyl) methyl anion compound. R3〇3 represents an organic group. The number of carbon atoms of the organic group represented by R3G3 is usually from 1 to 30 and preferably from 1 to 20. As for the organic group represented by R3()3, it may specifically be exemplified as R2G4 and 112 in the formula (ZII). The aryl group, the alkyl group and the cycloalkyl group shown in the designated examples of (5) The repeating unit (A) preferably has a structure in which an acid anion can be generated in a side chain of the resin upon irradiation with actinic rays or radiation. Selecting this structure limits the diffusion of the acid produced, and in resolution Improvement of the edge roughness is effectively preferred aspect A specified example of the display, but the present invention is not limited by its square -20-201107879 Ltd.) Almost 21 - Right Like

OH ^3⁄4)

-21- 201107879 -«^(0)3 ^θΜ〇+-)3 Articles •^eeH〇 Bu 1

Φ - Ό -c〇»eCM^ ^O^Xq -coFCK^, ecy〇

^ecMr

~^θ Φ,-(0)2 -%θ Μθ*Ή -5〇»ΘΦ'-(〇-Ή2 -&lt;丨-(〇)2 -00®Φ»-(〇-}-)2 — Co strict copy - 2 -22- 201107879

ΝΘ ο Λ f3co^°

The content of the repeating unit (Α) in the resin (Ρ) of the present invention is preferably in the range of 0.5 to 80 mol%, more preferably in the range of 1 to 60 mol%, and particularly preferably 2 to 40 in the total repeating unit. Mole% range. It may be used alone as a -23-201107879 repeating unit (A)' or two or more may be used in combination. The synthesis method of the monomer corresponding to the repeating unit (A) is not particularly limited', but a synthetic method of changing an acid anion having a polymerizable unsaturated bond of a corresponding repeating unit to a halide of a known gun salt can be exemplified. More specifically, a monomer corresponding to the target repeating unit (A) can be stirred by a metal ion salt (for example, sodium ion or potassium ion) of an acid having a polymerizable unsaturated bond of a corresponding repeating unit in the presence of water or methanol. Or an ammonium salt (ammonium, triethylammonium, etc.), and a key salt having a halogen ion (chloride ion, bromide ion, iodide ion, etc.) to carry out an anion exchange reaction, followed by separation and an organic solvent (for example, dichloromethane, Chloroform, ethyl acetate, methyl isobutyl ketone, tetrahydrofuran, etc. are synthesized by washing with water. Further, the monomer may be subjected to an anion exchange reaction by stirring the above compound in the presence of water in an organic solvent (for example, dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone, tetrahydrofuran, etc.) and water. And then synthesized for separation and water cleaning operations. The specified examples of the repeating unit (A) are shown below, but the present invention is by no means limited thereto. -24- 201107879 •-(ch2*ch}-* *-(ch2-ch}-*ο όΧθ|-〇)3 οη·)3 SC^€&gt;T〇c〇*-^ch2-ch]- * 1

• For example, 2 ^Q~々&quot;0)3 丫. -25- 201107879 . 如芬·.如-{i. 4—冬·c=o &lt;τ&quot;° θθ //=ν. f° Pj= •-(cHr 今+* mi

o\

如如. . 4卡 ‘十十·NOi ^%-Όΐ 疋 k-(cHr&lt;[4*· c=o 〇V?^3

-26- 201107879 ♦-(ch2-ch)-* *-(ch2-ch)-· *-(ch2-ch)-* c=〇 C=0 c=0

Vsof! Money V-, Pie); Hv-e *-{ch2-ch}-* *-^ch2-ch)-* •~(ch2-ch}-· #^ch2-ch^-* 1 OCHa) 5〇3θ©,_{0)2

•27- 201107879 mi i ^^y〇)2 °^Λγ?-〇)2 ^O), •-(〇Η,·&lt;ρ^-

^V

Such as Fen. 々〇),

*-{&lt;5Hr{-)-* fOpI . What?

, S0, *-{ch*-ch)-· *-(ch4-ch}^ c=o Bu V^^oi Ηχ^-ίο+ι -28- 201107879 co c=o co c=oc=oc= o » O-CHjCHjCH,-scf

-(.^-^4 (?-?-)- -(-c-c-)- «like.y £0〇?〇s^,-(〇) (4) 2

4f-f-)- έο,θ @5-{〇-°^\ c*〇 c=o 0H 0-CHjCH2CH2 -sof Φι~^^〇4Η8ι) 4|—J-)-

c»oc ? HN

(tH ό Φ w-

;pf®,_^Q.c4H.&gt;) ^90'-(OC c=o ^-CF, Ί QC CF2S〇3

Μ cf2sc^ % c=o I Θ O^^SOjNSCJjCFa

Θ CF2S0iNS02CF3 -29- 201107879

The repeating unit (A) may be a repeating unit having a nonionic acid generating moiety, such as the exemplified compounds (a31) to (al26) and (al45) to (Patent JP-A-1 0-22 1 8 5 2) Al96). The repeating unit (B) may use any repeating unit as long as it is a repeating unit containing a group which can be decomposed by the action of an acid and forms a carboxylic acid. It is preferred to use a repeating unit represented by the following formula (I) as the repeating unit (B).

R〇1 R〇2 \ C—C—)-* ( Ϊ ) I I /

R〇3 L In the formula (I) 'each R (n, R〇2 and R〇3 independently represent a hydrogen atom, a -30-201107879 group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxy group) Carbonyl group. Rq3 may also represent a pendant group and the bond L forms a 5- or 6-membered ring. L represents a single bond or a divalent bond (provided that when L bonds to form a 5 or 6-membered ring) Represents a trivalent linkage). The nucleus represents an alkyl group, and each of 〜 and 〜 independently represents a hydrogen atom, a aryl group, a ring-based group, or an aryl group. 1^2 and r3 may be bonded to each other to form a ring, provided that the condition is R2 and R3 do not represent a hydrogen atom. As for the alkyl group, the cycloalkyl group, the halogen atom, and the alkoxycarbonyl group represented by any of Roi to R〇3, R()4 to R()5 may be exemplified as described above. And the same group of rQ7 to R〇9. As for the divalent bond group represented by L, it can be exemplified as a stretching base, an aryl group, an aralkyl group, -COO-L!-, -OL!- And a combination formed by combining two or more of the above. L! represents an alkylene-cycloalkylene group, an aryl group, or an aralkyl group. L is preferably a single bond, -COO-Li- (Li is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group a propyl group or an aryl group. The alkyl group represented by any of Ri to R3 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and Particularly preferred is an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tributyl. The cycloalkyl group preferably has 1 to 20 carbon atoms, which may be a monocyclic ring such as a cyclopentyl group or a cyclohexyl group, or may be a polycyclic ring such as a norbornyl group, a tetracyclononyl group or a tetracyclic group Carbon-based), but more preferably a monocyclic ring from the viewpoint of stability in a photoresist solvent. -31- 201107879 A ring formed by bonding R2 and R3 to each other preferably has 3 to 20 carbon atoms' which can be a single a ring (such as a cyclopentyl group or a cyclohexyl group), or may be a polycyclic ring (such as a norbornyl group, a tetracyclic fluorenyl group or a tetracyclododecanyl group), but is more preferably a viewpoint of stability in a photoresist solvent. Monocyclic ring. When R2 and r3 are bonded to each other to form a ring, '1 preferably represents an alkyl group having from 丨 to 3 carbon atoms, and more preferably represents a methyl group or an ethyl group. The aryl group represented by each of R2 and r3 Preferably, it has 6 to 20 carbon atoms', and examples thereof are phenyl and naphthyl. When R2 or R3 represents - represents a hydrogen atom, the other is preferably an aryl group. The repeating unit (B) is in the resin (p). The content is preferably in the range of from 5 to 90 mol% of all repeating units, more preferably in the range of up to 8 Torr, and still more preferably in the range of from 20 to 70 mol%. A repeating unit (B) may be used, or two or more may be used in combination. The method of synthesizing the monomer corresponding to the repeating unit (B) is not particularly limited, and a general synthetic method containing a polymerizable ester may be used. A specified example of the repeating unit (B) is shown, but the invention is not limited thereto. -32- 201107879

(I-l)

-33- 201107879

-34- 201107879

-35- 201107879

-36- 201107879

-37- 201107879

(I-98) Ο

Any repeating unit can be used as the repeating unit (c) as long as it is a repeating unit containing a carbon-carbon unsaturated bond. Even when the repeating unit (A) contains a carbon-carbon unsaturated-38-201107879 bond, this case is not included in the repeating unit (C). The repeating unit (C) is preferably a repeating unit represented by the following formula (II). .

/ R〇1 R〇2

I I *-c-c-

\ I I

R〇3 Q In the formula (II), Roi'Ru and Rm have the same meanings as described in the formula (I)' and Q represents a group containing a carbon-carbon unsaturated bond. In the formula (II), each R〇1 'Rg2 and Re»3 preferably represents a hydrogen atom, and Q preferably represents an aromatic ring-containing group, and more preferably has 1 to 20 carbon atoms substituted. Or unsubstituted aromatic group. Examples of the aromatic group herein include the following: phenyl, naphthyl, anthracenyl, phenanthryl, benzyl-triphenyl, fused tetraphenyl, biphenyl, pyrrolyl, furyl, thienyl, imidazolyl, cacao Azyl, thiazolyl, pyridyl, pyridyl, pyrimidinyl, pyrene, sulfonyl, benzofuranyl, benzothienyl, isobenzofuranyl, quinolinyl, quinolinyl, anthracene Well base, dihydronaphthyl, quinoxalinyl, quinazolinyl, isoquinolinyl, oxazolyl, acridinyl, morpholinyl, thioxyl, ketenyl, stellate, benzene And the mountain star base, benzothiazepine base, and the brown well base. Among these aromatic groups, an aromatic ring is preferred, and a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group are more preferable, and still more preferably a phenyl group (benzene ring). When the resin (P) is composed only of the repeating unit (A) and the repeating unit (C), the repeating unit (C) is preferably a repeating unit represented by the following formula (II-1).

8—^-* (E-1)

Q Q represents a group containing a carbon-carbon unsaturated bond. The content of the repeating unit (C) in the resin (P) is preferably in the range of from 5 to 90 mol% of the total repeating unit -39 to 201107879, more preferably in the range of (to 8 Torr), and still more Preferably, it is in the range of 20 to 70 mol%. It may be used alone or in combination of two or more, but preferably at least one derived from hydroxystyrene (preferably The hydroxy styrene is a hydroxy styrene derivative, and examples thereof include hydroxy styrene containing a fluorine-substituted alcohol substituent. In the present invention, the composition ratio of the repeating unit (C) (mole) Preferably, it is equal to or higher than the composition ratio of the repeating unit (B). The repeating unit having the carbon-carbon unsaturated bond in the repeating unit (8) is also included in the repeating unit (c)e corresponding to the repeating unit (C) The synthesis method of the monomer is not particularly limited 'but the monomer can be synthesized by referring to a synthesis method of an aromatic compound containing a polymerizable carbon-carbon double bond, which is described, for example, in J. Med. Chem., 34 (5) Vol. 1, 1675-1692 (1991), ibid., vol. 35 (25), 4665-4675 (1992) J. Org. Chem., Vol. 4 5 (18), 3 6 5 7 - 3 6 64 (1 9 80), Adv. Synth. Catal., Volume 349 (1-2), 1 52- 1 56 (2007), J. Org. Chem., vol. 28, 1 9 2 1 - 1 9 2 2 (1 963), Synth. Commun., vol. 28 (15), 2677-2682 (1989), and The synthesis method listed in the document. The following shows a specified example of the repeating unit (c) in the resin (P) 'But the invention is not limited thereto. In the formula, a represents an integer from 0 to 2. -40&quot; 201107879

〕Γ(0Κ&gt;» (Π·9&gt;

(Π-21)

(0.23)

(11-2 4) (Π.25)

(1-3 5) (11.34) 41 201107879

(Π·36)

(Π-4 1 )

-τ-ίΟΗ),

OCH, (Π-47)

&lt;Π·4 8) (ϋ·4 6> ,Η&gt;· 十(〇Η)·

Irw. ο (Π-6 3) (Π-5 1:

(〇Η). α (π-5 6) OCH, (H-62)

I C0-58)

Η--F ΟΗ (H — 61)

F--F ΟΗ (Liaoyi 62)

(H-63) (Π-64) (Π-65) -42- 201107879 The resin of the present invention preferably further contains (D) a unit which has a function of disintegrating and increases the dissolution rate in the alkali developer. And its system is represented by the following formula (All):

COO-Ab-V In the formula (All), Rb〇 represents a hydrogen atom, a halogen atom or preferably has 1 to 4 carbon atoms). The alkyl group represented by Rb〇 may have a preferred substituent hydroxyl group and a halogen atom. Examples of the halogen atom represented by Rb 氟 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Its preference is methyl, hydroxymethyl, and trifluoromethyl, and particularly preferably methyl.

Ab represents a single bond, an alkyl group, a monocyclic or polycyclic alicyclic divalent bond, an ether bond, an ester bond, a carbonyl group, or a combination of these groups, and is preferably a single bond or a -ΑΙμ-( The divalent AIM represented by : 02_ represents a linear or branched alkyl group, or a monocyclic or polycyclic ring, and is preferably a methylene group, an ethyl group, a cyclohexylene group, a gold group or a pendant alkyl group. It is a group which can be decomposed by the action of an alkali developer and which increases the dissolution rate in the agent, preferably a group having an ester bond, and a group having a lactone structure. As for a group having a lactone structure, any of them can be used. Has a basis, but is preferably a repeat of the base development with a 5- to 7-membered ring lactone structure

An alkyl group (more, an exemplified example thereof, which is preferably a divalent bond between a hydrogen atom and a hydrocarbon structure. A cycloalkylalkyl group, a base developed and a better lactone structure, and more than -43 - 201107879 Preferably, the 5- to 7-membered ring lactone structure of the other ring structure is condensed in the form of a bicyclic structure or a helical structure. More preferably, it has a formula (LC1-1) to (LC 1- 17) Any repeating unit of the lactone structure represented by the lactone structure. The lactone structure may directly bond the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1- 6), (LC1-13), (LC1-14), and (LC1-17).

(Rb2}n2 (Rbjn2 (Rb2)n2

The lactone moiety may or may not have a substituent (Rb2). With respect to a preferred substituent (Rb2), it is exemplified by an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and having 2 to 8 The alkoxycarbonyl group of a carbon atom, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group, and more preferably a substituent is an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. N2 represents an integer of 0 to 4" When 112 is 2 or more, each substituent may be the same or different from each other. A plurality of substituents (Rb2) may be bonded to each other to form a ring. -44- 201107879 The repeating unit having a lactone group usually has an optical isomer, and any optical isomer can be used. It may be used alone or in combination with a plurality of optical isomers. The optical purity (ee) is preferably 90% or more, and more preferably 95% or more, when an optical isomer is mainly used. The content of the repeating unit (D) in the resin (P) is preferably from 0.5 to 80 mol% of the total repeating unit, more preferably from 1 to 60 mol%, and still more preferably 2 Up to 40% of the range. It may use one type of repeating unit (D) alone, or two or more types may be used in combination. The use of the specified lactone structure improves line edge roughness and development defects. The specified examples of the repeating unit (D) in the resin (P) are shown below, but the invention is not limited thereto. In the formula, Rx represents H, CH3, CH2〇h' or C F 3 〇 -45- 201107879

The resin (p) of the present invention may be in the form of random, block, sparse, and star forms. The resin (P) (containing the repeating units (A) to (C) or (A) to (D)) according to the present invention may be, for example, a radical polymerization, a cationic polymerization, or an anion of an unsaturated monomer corresponding to each structure. Sexual polymerization synthesis. The target resin can also be obtained by polymerizing an unsaturated monomer corresponding to the precursor of each structure and then performing a polymerization reaction. The molecular weight of the resin (P) of the present invention is not particularly limited, but the weight average of -46 to 201107879 is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 1,5 to 20,000, and particularly Good for 2,000 to 1 〇, the range of 〇〇〇. The weight average molecular weight of the resin is here shown as the molecular weight of polystyrene as measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)). The polydispersity (Mw/Mn) is preferably from 1.00 to 5.00, more preferably from 1.03 to 3.50, and still more preferably from 1.05 to 2.50. For the purpose of improving the properties of the resin, the resin (P) of the present invention may further contain a repeating unit derived from other polymerizable monomers as long as the dry etching resistance is not significantly impaired. The content of the repeating unit derived from the other polymerizable monomer in the resin is usually 50 mol% or less of the total repeating unit, and is preferably 30 mol% or less. Other useful polymerizable monomers include the following: For example, the polymerizable monomer includes a compound having an addition polymerizable unsaturated bond selected from (meth) acrylate, (meth) acrylamide, allyl compound , vinyl ether, vinyl ester, styrene, and crotonate. Specifically, as for the (meth) acrylate, examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and tert-butyl (meth) acrylate, ( Amyl methacrylate, cyclohexyl (meth) acrylate ethyl hexyl (meth) acrylate, octyl (meth) acrylate, third octyl (meth) acrylate, (meth) acrylate 2 - chloroethyl ester, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, and phenyl (meth)acrylate. As for (meth) acrylamide, an example thereof is (meth) propylene hydride - 47 - 201107879 amine, N-alkyl (meth) acrylamide (alkyl group is an alkyl group having 1 to 1 carbon atom) , for example, methyl, ethyl, propyl, butyl, tert-butyl, heptyl, octyl, cyclohexyl, benzyl, hydroxyethyl, benzyl, etc.), N-aryl (meth) propylene oxime Amine (aryl group is, for example, phenyl, tolyl, nitrophenyl, naphthyl, cyanophenyl, hydroxyphenyl, carboxyphenyl, etc.), N,N-dioxane (meth) acrylamide ( The alkyl group is an alkyl group having 1 to 10 carbon atoms 'e.g., methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl, etc.), N,N-diaryl(methyl)propene oxime Amines (aryl groups such as phenyl), N-methyl-N-phenylpropenylamine, N-hydroxyethyl-N-methylpropenylamine, and N-2-acetamidoethyl-N - Ethyl acrylamide. As the allyl compound, examples thereof include allyl esters (e.g., allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, benzene) Allyl formate, allyl acetate, allyl lactate, etc.), and allyloxyethanol. As the vinyl ether, an example thereof is an alkyl vinyl ether (e.g., hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxy group). Ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethyl a diol vinyl ether 'dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofuranyl vinyl ether, etc.), and Vinyl aryl ether (eg vinyl phenyl ether, vinyl methyl ether, vinyl chlorophenyl ether) vinyl 2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl decyl ether, etc. ). -48- 201107879 As for the vinyl ester, examples thereof include vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate. , dichlorovinyl acetate, methoxy vinyl acetate, butoxy vinyl acetate, phenyl vinyl acetate, ethylene glycol vinyl acetate, vinyl lactate, vinyl β-phenylbutyrate, chlorohexylcarboxylic acid Vinyl ester, vinyl benzoate, vinyl laurate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like. As the crotonate, an example thereof is an alkyl crotonate (e.g., butyl crotonate, hexyl crotonate, glycerol monocrotonate, etc.). As the dialkyl isonic acid, examples thereof include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. As the dialkyl ester of maleic acid or fumaric acid, examples thereof include dimethyl maleate, dibutyl fumarate and the like. In addition to the above, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, and maleonitrile are exemplified. Further, an addition polymerization unsaturated compound which can be copolymerized with a repeating unit according to the present invention can be used without particular limitation. The resin (ρ) of the present invention may be used alone or in combination of two or more. The content of the resin (ρ) is preferably from 30 to 100% by mass, more preferably from 50 to 100% by mass, and particularly preferably from 70 to 100% by mass based on the total solid content of the sensitized ray or radiation sensitive resin composition of the present invention. %. As a specific example of the resin (Ρ), which exemplifies a repeating unit having one or more selected examples selected from the formulae (III) to (V) / one or more repeating units selected from the specified examples of the formula (I) / A plurality of resins selected from the repeating -49-201107879 unit of the specified example of formula (II). In particular, it is preferred that the resin (P) consists of only repeating units (A) to (C) or only repeating units (A) to (D), and all repeating units (C) are of the formula (H). · 1) Repetition unit indicated. The repeating unit (C) may comprise one or more repeating units represented by the formula (η·Π. In the resin (Ρ), it is also preferred that the proportion of the repeating unit having a ring structure in the main chain is 3 〇 mass% or It is smaller 'and it is more preferably completely free of this repeating unit. The following shows a better specified example of the resin (Ρ)', but the invention is not limited thereto. -50- 201107879

201107879

-52- 201107879

+P —Λο ΟΎΙΟ o ^- 5 *09&quot;%H°- dr^f-iot

§ diGM^4-^^8-^^^

Ff nl&amp;

SN-C0 &lt;wNi&gt; uwi {m -53- 201107879

β

^.s &lt;wei ;?&amp; s£ f-3^

Fgi flot SI χβίι

T3-fs^si 3, β i^i^tt^ ο (esi

s X arai f-lrt f i -54- 201107879

-55- 201107879 Outside rtrhrf^r

萃6 3⁄4} +Q ο OS is I" HO&^?ol&gt; Il^nMH^IOOO nxeo

Outside - (Ns_d&gt; ?ni &lt;es-a 5°丄) 9^;e leaves ru&gt;?

Ab B 十·fr^' &lt;ec-s

PIS ^ so-l ifot

(snld t-iotflo}·

Qn,d) -56- 201107879 /βφ

«noso^xwNXSONXOO l$cos ΙΘ°

*ί°. κAt -φι-δ) l-&lt;&gt;lf-ir^4 fips image. s/04-γ γf tTrttht

¢3⁄4 ΗΟ (w(o-d&gt; (inch©i) (θω? (oi-i

Isl 1{!0}(1 &quot;v^s^o'o ^-^-0^0^-0tr^tnt t:r4 :5?.^. f2° flout!

HO f-lot (s,

CIC 3 &quot;&amp;, § HO ^\vJ3+UCJ xoιίϋ r°-^/ 一—)严 I』 010 ti^

U9i) -57 201107879 汁晷介 Nirtb^f-lr}?^ΧΙ4'^ ”($ &quot;isw*o%is··

&quot;0$0 ^it nwu«o Φ b

&lt;~Bu 4 nbrto? ; i Φr^4介rfl£¥-δ; f "This ot5E i -U.&amp;

斯卜i (Bub-&amp;-58-201107879 The photosensitive ray or radiation-sensitive resin composition of the present invention contains a solvent having a normal pressure (760 mmHg) boiling temperature of 150 ° C or lower. One may be used in combination at a normal temperature boiling temperature of 150 ° C or more, or two or more may be used in combination. Further, a solvent having a boiling temperature of more than 150 ° C at a normal pressure may be used in combination. In the composition of the present invention, the boiling temperature is 1 The content of the solvent of 50 ° C or lower is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably; ί to 100% by mass or more, particularly preferably 75 mass % or more, and is 90% by mass or more. The boiling temperature of the solvent having a boiling temperature of 150 ° C or lower is preferably J to 150 ° C, and more preferably 80 to 150 ° ° C. The solvent having a boiling temperature of 150 ° C or lower is preferably an organic solvent and the organic solvent may be selected, for example, from alkylene glycol monoalkyl ether carboxylate, alkyl ether monoalkyl ether, alkyl lactate, and C. An acid alkyl alkoxylate, a cyclic ketone, a cyclic monoketone compound, an alkylene carbonate, an alkyl alkoxylate, and an acid alkyl ester. For example, a solvent is selected in a solvent having a boiling temperature of 150 ° C or lower, and one or two or more may be a mixture, and the solvent may be combined at a normal temperature boiling temperature of more than 1 500. Incidentally, the solvent is exemplified below, and the boiling temperature is not normal with respect to the pressure. Further, when the boiling temperature of the force other than 760 mm mercury is described, it means that the solvent has a high boiling temperature. a solvent, and the solvent is shown to be at a temperature of more than 150 ° C at 760 mm Hg. The total amount i 70 is the best i 50 in the small one, and the alkane has the pressure of the acetone from the use agent. Boiling-59-201107879 As for the alkylene glycol monoalkyl ether carboxylate, a preferred example is propylene glycol monomethyl ether acetate (PGMEA, 1-methoxy-2-ethoxypropane propane) (bp) : 146 ° C), propylene glycol monoethyl ether acetate (bp ·: 164-165 ° C), propylene glycol monopropyl ether acetate (bp: 1 73- 1 74 ° C / 740 mm Hg), ethylene glycol Methyl ether acetate (bp: 143 ° C), and ethylene glycol monoethyl ether acetate (bp ·: 156 〇 C). As the alkylene glycol monoalkyl ether, preferred examples are propylene glycol monomethyl ether (PGME, 1-methoxy-2-propane) (bp: 119 ° C), propylene glycol monoethyl ether (bp ·: 130- 131. (:), propylene glycol monopropyl ether (bp: 148 〇 C), propylene glycol monobutyl ether (bp: 169-170. (:), ethylene glycol monomethyl ether (bp: 124-125 ° C) With ethylene glycol monoethyl ether (bp: 1 3 4- 1 3 5 〇C). Preferred examples of the alkyl lactate are, for example, methyl lactate (bP·: 145〇C), ethyl lactate (bp·: 154°C), propyl lactate (bp: 1 69- 1 72 ° C), With butyl lactate (bp: 1 8 5 - 1 8 7 ° C). As the alkyl alkoxylate propionate, preferred examples thereof are ethyl 3-(ethoxy) propionate (bp·: 1 69- 1 70 ° C), methyl-3-ethoxypropionate (bp) : 138-141 ° C), with ethyl-3-methoxypropionate (bp·: 156-158 ° C). As the cyclic lactone, preferred examples thereof are β-propiolactone (b. p ·: 162 ° C), p-butyrolactone (bp: 71-73 ° C / 29 mm Hg), γ·丁内Ester (bp: 204-205 °C), α-methyl-γ-butyrolactone (bp·: 78-81 °C/10 mm permanent), β-methyl-γ-butyrolactone (bP·: 87-88 ° C / 1 〇 mm Yong), γ-valerolactone (bp: 82-85 ° C / 10 mm Hg), γ · caprolactone (bP ·: 219 ° c), γ-octanolactone (bp·: 234 ° C), and α-hydroxy-γ-butyrolactone (bp: 133 ° C / 10 mm Hg). -60-201107879 As for the monoketone compound which may have a ring, preferred examples thereof are 2-butanone (bp: 80 ° C), 3-methylbutanone (bp: 94-95. 〇, tertiary butyl) Ethyl Ethyl Ketone (bp: 106 ° C), 2-pentanone (bp·: 101-105 ° C), 3-pentanone (bp: 102 ° C), 3-methyl-2-pentanone (bp· : 118°C), 4-methyl-2-pentanone (bp·: 117-118°C), 2-methyl-3-pentanone (b.p_: 113°C), 4,4-di Methyl-2-pentanone (bp: 1 2 5 - 1 30 ° C) ' 2,4-dimethyl-3-pentanone (bp: 124. 〇, 2.2.4.4-tetramethyl-3- Pentanone (bp: 1 5 2- 1 5 3 ° C), 2-hexanone (b_p.: 127 ° C), 3-hexanone (bp: 123 ° C), 5-methyl-2-hexanone (bp·: 145°C), 2-heptanone (bp: 149-15 (TC), 3-heptanone (bp: 1 46- 1 48 ° C), 4·heptanone (bp: 145 ° C) , 2-methyl-3-heptanone (b_p.: 1 5 8 - 1 60 ° C), 5-methyl-3-heptanone (bp: 161-162 ° C), 2,6-dimethyl -4-heptanone (bp·: 1 65- 1 70 ° C), 2-octanone (bp: 173 ° C), 3-octanone (bp: 167-168 ° C), 2-nonanone (bp) : 192 ° C / 743 mm Hg), 3-fluorenone (bp: 1 87- 18 8 ° C), 5-nonanone (bp ·: 1 8 6- 1 8 7 ° C) 2-nonanone (bp: 211 ° C), 3-fluorenone (bp: 2 04 -2 0 5 ° C), 4 fluorenone (b.p_: 206-207. (:), 5-hexene- 2-ketone (bp·: 1 28 - 1 29 ° C), 3-penten-2-one (bp: 12 b 124 ° C), cyclopentanone (bp··· 130-131 ° C), 2 -methylcyclopentanone (b.p_·· 139〇C), 3-methylcyclopentanone (bp·: 145°C), 2,2-dimethylcyclopentanone (bp: 1 43 - 1) 4 5 °C), 2.4.4-trimethylcyclopentanone (bp: 160 °C), cyclohexanone (bp: 175 ° C), 3-methylcyclohexanone (b_p.: 1 69- 1 70. 〇, 4-methylcyclohexanone (bp·: 169-171 ° C), 4-ethylcyclohexanone (bp·: 1 92- 1 94). ":), 2,2-dimethylcyclohexanone (bp: 169-170 ° C), 2,6-dimethylcyclohexanone (bp: 1 74- 1 76 ° C), 2, 2, 6-trimethylcyclohexanone (bp: 1 7 8 - 179 ° C), cycloheptanone (bp: 179 ° C), 2-methylcycloheptanone (bp·: 1 82- 1 8 5 ":), and 3-A-61- 201107879 Cycloheptanone (bp: 100 ° C / 40 mm pro). As the alkylene carbonate, preferred examples thereof are propylene carbonate (bp: 240 ° C), and ethylene carbonate (bp: 162. 〇, ethyl carbonate (bp,: 243-244 ° C / 740 mm Hg), with butyl carbonate (bp: 88 ° C / 0.8 mm Hg). As for the alkyl alkoxylate, a preferred example is 2-methoxyethyl acetate (bp: 145 °) C)' 2-Ethyl acetate (b.p_: 1 5 5 - 1 5 6 °C), 2-(2-ethoxyethoxy)ethyl acetate (bp: 219.C) And 1-methoxy-2-propyl acetate (bp: 1 45- 146 ° C)» As for the pyruvate alkyl ester, a preferred example is methyl pyruvate (bp: 134-137 ° C), Ethyl pyruvate (bp: 144 ° C), and propyl pyruvate (bp ·: 1 66 ° C) » As for the solvent which can be preferably used, it is exemplified as 2-heptanone, cyclopentanone, γ-butyl Lactone, cyclohexanone, butyl acetate, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl-3-ethoxypropionate, pyruvic acid Ethyl ester, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, and propyl carbonate It is a solvent which lowers the degassing, and is particularly preferably a solvent having a boiling temperature of 150 ° C or lower at normal pressure, such as 2-heptanone, propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether. The amount of use in the total amount of the material (including all solvents having a boiling temperature of 150 volts or higher and 150 ° C or lower) can be arbitrarily adjusted according to the desired film thickness or the like, but is usually adjusted so that the composition The concentration of all the solid content is from 0.5 to 30% by mass, preferably from 1. 〇 to 20% by mass, and more preferably from 1.5 to 10% by mass. -62- 201107879 The sensitization of the present invention The radiation or radiation sensitive resin composition may further contain a basic compound, a resin which is decomposed by an action of an acid to increase a dissolution rate in an aqueous alkali solution, a conventional photoacid generator, a surfactant, an acid decomposable dissolution inhibiting compound, A dye, a plasticizer, a sensitizer, a dissolution accelerating compound in a developer, and a compound having a proton-accepting functional group 〇 &lt;alkaline compound&gt; Preferably, the sensitized ray or radiation sensitive resin composition of the present invention further contains Alkali The basic compound is preferably a nitrogen-containing organic basic compound. The usable compound is not particularly limited, and it is preferred to use, for example, a compound classified as the following (1) to (4). a compound represented by the following formula (BS-1)

R I (BS-1)

R - N - R In the formula (BS-1), each R independently represents a hydrogen atom, an alkyl group (straight chain or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group, and an aralkyl group. Either. However, the three R are not all hydrogen atoms. The number of carbon atoms of the alkyl group represented by R is not particularly limited, and is usually from 1 to 20, and preferably from 1 to 12. The number of carbon atoms of the cycloalkyl group represented by R is not particularly limited, and is usually from 3 to 20, and preferably from 5 to 15. The number of carbon atoms of the aryl group represented by R is not particularly limited, and is usually from 6 to 20, and preferably from 6 to 10. Specifically, the example -63-201107879 shows phenyl and naphthyl. The number of carbon atoms of the aralkyl group represented by R is not particularly limited and is usually from 7 to 20, preferably from 7 to Π. Specifically, its benzyl group. The alkyl group, the cycloalkyl 'aryl group, and the aralkyl group represented by R may be substituted with a substituent. As the substituent, an alkyl group, a ring, an aryl group, an aryl group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an alkoxy group, and an alkoxycarbonyl group are exemplified. Preferably, in the compound represented by the formula (BS-1), three R represent a hydrogen atom, or all of R are not a hydrogen atom. As a designated example of the compound represented by the formula (BS-1), examples thereof include n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine cyclohexylmethylamine, and tetradecylamine. , pentadecylamine, hexadecylamine, decaamine, diamine, methyl octadecylamine, dimethylundecylamine, N, N. decylamine, methyl octadecylamine , N,N-dibutylaniline, dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tris(tri)aniline. The formula (BS-1) exemplifies one of at least one of R is a hydroxyalkyl group-containing compound as a preferred embodiment. As specified, triethanolamine and N,N-dihydroxyethylaniline are exemplified. Further, the alkyl group represented by R may have oxygen in the alkyl chain. The atom is an oxygen-extended alkyl chain. The oxygen alkyl chain is preferably -CH2CH20-. As for the example 'exemplified ginsyl (methoxyethoxyethyl) amine, and US Patent No. 6,040,112, the third In the column, the combination disclosed below in line 60, and the exemplification of the hydrogenoalkylalkylcarbonyl group, only the N, N-"yl" substituents form the designated adinote. -64- 20110 7879 (2) A compound having a nitrogen-containing heterocyclic structure as a heterocyclic structure, which may or may not have an aromatic character. Further, it may contain a plurality of nitrogen atoms, and may contain a hetero atom other than nitrogen. Specifically, it is exemplified A compound having an imidazole structure (for example, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole), a compound having a piperidine structure (for example, N-hydroxyethylpiperidine, hydrazine (1, 2) , 2,6,6-pentamethyl-4-piperidinyl) sebacate, a compound having a pyridine structure (for example, 4-dimethylaminopyridine), and a compound having an antipyrine structure (e.g., antipyrine, hydroxyantipyrine). It is also preferred to use a compound having two or more ring structures. Specifically, it exemplifies 1,5-diazabicyclo[4.3.0]壬-5-ene and 1,8-diazabicyclo[5.4.0]-undec-7-ene. (3) Amine compound having a phenoxy group. The amine compound having a phenoxy group is an amine compound. a compound having a phenoxy group at the terminal of the opposite side of the nitrogen atom of the alkyl group. The phenoxy group may have a substituent such as an alkyl group, an alkoxy group, or a halogen group. An atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, a decyloxy group, or an aryloxy group. More preferably, the compound is a phenoxy group and a nitrogen atom. A compound having at least one oxygen alkyl chain therebetween. The number of oxygen alkyl groups in one molecule is preferably from 3 to 9, and more preferably from 4 to 6. The oxygen alkyl chain is preferably - CH2CH20-. As a designated example, it is exemplified by 2-[2-{2-(2,2-dimethoxyphenoxyethoxy)ethyl}-daily (2-methoxyethyl)]amine, And U.S. Patent Application No. -65-201107879, No. 2007/02245, No. 9A1, [0066], (C1 -3). (4) Money salt It is also arbitrarily used as an ammonium salt. A preferred compound is a hydrogen salt. More specifically, it is preferably tetrabutylammonium hydroxide tetraammonium hydroxide. As the other basic compound, a compound synthesized by the JP-A patent, and a compound disclosed in paragraph § JP-A-2007-298569 can also be used. The basic compound is used singly or in the group of two or more. The amount of the basic compound is usually from 0.001 to 10, preferably from 0.01 to 5% by mass based on the total solid content of the sensitizing ray or the sensitizer. The molar ratio of the acid generator/basic compound is preferably 2. From the viewpoint of sensitivity and resolution, the molar ratio is preferably: and the viewpoint of suppressing the deterioration of aging due to exposure to heat treatment is It is preferably 30,000 or less. Preferably, it is 5.0 to 200, and still more preferably 7.0 to 150. The above-mentioned molar ratio of the acid generator is the total amount of the acid generator described later in addition to the I resin (P) contained in the resin (P). &lt;Dissolved by an acid to increase dissolution in an aqueous alkali solution In addition to the resin (P), the sensitizing ray or the sensitized article of the present invention may contain a resin which is decomposed by an action of an acid to increase the rate of alkali. Compound (C1-1) to oxide or carboxylic acid represented by hydrogen peroxide l-2002-3 63 1 46 Tiger patent, [0 1 0 8] used together. The amount of radiation resin is %, and is more than 5 to 300. That is, 2.5 or more pattern thickening causes this molar ratio to be more ohmic unit (a) and f-rate resin> Dissolving in the aqueous solution of the radiation resin group -66- 201107879 It can be decomposed by the action of acid and increased in the aqueous alkali solution The dissolution rate resin (hereinafter also referred to as "acid-decomposable resin") is a group which has a decomposable group due to the action of an acid and which generates an alkali-soluble group in the main chain or side chain of the resin or the main chain and the side chain (acid can be used) Decomposition base) resin. More preferably, it is a resin having an acid decomposable group in a side chain. The acid-decomposable resin can be reacted with an alkali-soluble resin and an acid-decomposable group, as disclosed in European Patent No. 254,853, JP-A-2-25850, JP-A-3-223860, and JP-A-4251259. Precursor, or by copolymerizing an alkali-soluble resin monomer with various monomers. As the acid-decomposable group, it is preferably, for example, a hydrogen which is substituted with an alkali-soluble group (e.g., a -CO0 group or an alkali-soluble group of -OH) in a resin having an alkali-soluble group by a group which is detachable by an action of an acid. The base of the atom. As the acid-decomposable group, specifically, the same group of the acid-decomposable group (for example, an acid-decomposable group described as the repeating unit (B) in the resin (P)) in the above-mentioned resin can be preferably exemplified. The alkali-soluble resin is not particularly limited. Examples thereof include a hydroxystyrene structure (for example, poly(o-hydroxystyrene), poly(m-hydroxystyrene), poly(p-hydroxystyrene), a copolymer thereof, hydrogenated poly(hydroxystyrene), having the following An alkali-soluble resin of poly(hydroxystyrene) having a substituent represented by any one of the structures, a phenolic hydroxyl group, a styrene-hydroxystyrene copolymer, an α-methylstyrene-hydroxystyrene copolymer, and hydrogenation A resin of a phenol resin, and an alkali-soluble resin containing a repeating unit having a carboxyl group such as (meth)acrylic acid or norbornenecarboxylic acid. -67- 201107879

The alkali dissolution rate of these alkali-soluble resins is preferably 170 Å/sec or more, particularly preferably 330 Å/sec or more, measured at 23 ° C with 2.38 mass% of tetramethylammonium hydroxide (TMAH). More specifically, the alkali dissolution rate can be obtained by dissolving the alkali-soluble resin alone in a solvent such as propylene glycol monomethyl ether acetate (PGMEA) to prepare a composition having a solid content concentration of 4% by mass. The film was coated on a silicon wafer to have a film (thickness: 1 Å nanometer), and the time until the film was completely dissolved in the TMAH aqueous solution (seconds) was measured. The content of the acid decomposable group is represented by the equation χ/(χ + γ), and the number of repeating units having a group which is decomposable by an acid action in the resin is (X), and has no effect due to acid. The amount of the repeating unit of the isolated base-protected alkali-soluble group is (Υ)»this content is preferably from 0.01 to 0.7, more preferably from 0.05 to 0.50, and still more preferably from 0.05 to 0.40. The weight average molecular weight of the acid-decomposable resin such as GPC polystyrene-68*201107879 is preferably 50,000 or less, more preferably 1,000 to 20,000, and particularly preferably 1, 〇〇〇1 Hey, hey. The polydispersity (Mw/Mn) of the acid-decomposable resin is preferably from 1.0 to 3.0, more preferably from 1.05 to 2.0, and still more preferably from 1.1 to 1.7» which may be used in combination with two or more acid-decomposable resins. In the sensitized ray or radiation sensitive resin composition of the present invention, the amount of the acid-decomposable resin blended in the composition (excluding the resin (P)) is preferably from 〇 to 70% by mass based on the total solid content of the composition. More preferably, it is 0 to 50% by mass, and still more preferably 〇 to 30% by mass. &lt;Acid generator&gt; The sensitized ray or sensitizing tree _ composition of the present invention contains a resin (P) having a photoacid generating structure, and in addition to the resin (P), the composition may contain an actinic ray Or a low molecular weight compound (hereinafter also referred to as an "acid generator") which generates an acid upon irradiation with radiation. As the acid generator, a photoinitiator for cationic photopolymerization, a photoinitiator for radical photopolymerization, a photodecolorizer for a dye, a photochromic agent, and when irradiated with actinic rays or radiation can be arbitrarily selected and used. Known compounds which produce acids, and mixtures thereof. Examples thereof include a diazonium salt, a scale salt, a phosphonium salt, a phosphonium salt, a sulfonium iminosulfonate, an anthracene sulfonate, a diazodiazine, and an o-nitrobenzyl sulfonate. For a reference example, reference may be made to the compounds disclosed in U.S. Patent Application Serial No. 2008/0241737 A1, [0164] to [0248]. When an acid generator other than the resin (P) having a photoacid generating structure is used for the sensitized ray or radiation sensitive resin composition of the present invention, the acid generator-69-201107879 may be used alone or in combination. Two or more. The content of the acid generator in the composition is preferably from 0 to 20% by mass, more preferably from 〇 to 1% by mass, and still more preferably from 〇 to 7% by mass, based on the total solid content of the photoresist composition. The acid generator is not important to the present invention, but it is used in an amount of usually 0.01% by mass or more in order to obtain the effect of the addition. &lt;Interacting Agent&gt; It is preferred that the sensitized ray or radiation sensitive resin composition of the present invention further comprises a surfactant. Preferably, the surfactant is a fluorine/ruthenium interfacial surfactant. As such a surfactant, MEGAFAC F176, MEGAFAC R08 (manufactured by Dainippon Ink and Chemicals Inc.), PF 6 5 6 'PF 6 3 2 0 (manufactured by OMNOVA Solution Inc.), Troy Sol S-3 66 (Troy Chemical) are exemplified. Co., Ltd., manufactured by Fluorad FC430 (manufactured by Sumitomo 3M Limited), and polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.). Surfactants other than fluorine/ruthenium surfactants can also be used. More specifically, it exemplifies a polyoxyalkylene ether and a polyoxyalkylene aryl ether. In addition to the above, it is possible to use a known surfactant. As for other useful surfactants, it is exemplified by the surfactants disclosed in U.S. Patent Application Publication No. 2008/0248425A1, [0273]. The surfactant may be used alone or in combination, the amount of the surfactant to be used may be preferably 0.0001 to 2% by mass based on the total solid content of the photosensitive ray or the radiation-sensitive resin group-70-201107879. More preferably, it is 0.001 to 1% by mass»&lt;acid-decomposable dissolution inhibiting compound&gt; The photosensitive ray or radiation-sensitive resin composition of the present invention may contain a molecular weight of 3,000 or less, which is decomposable by the action of an acid. A dissolution inhibiting compound (hereinafter also referred to as "dissolution inhibiting compound") which increases the dissolution rate in the developer. The dissolution inhibiting compound is preferably an alicyclic or aliphatic compound containing an acid-decomposable group such as the acid-decomposable cholic acid derivative described in Proceeding of SPIE, 2724, 355 (1996). As the acid-decomposable group and the alicyclic structure, the same compound as the above acid-decomposable resin can be exemplified. When the sensitized ray or radiation sensitive resin composition of the present invention is irradiated with an electron beam or EUV rays, it is preferred to use a dissolution inhibiting compound having a structure in which a phenolic hydroxyl group of a phenol compound is substituted with an acid decomposable group. The phenol compound preferably has from 1 to 9 phenol structures, and more preferably from 2 to 6 phenol structures. The solubility-inhibiting compound of the present invention has a molecular weight of 3,000 or less, preferably 300 to 3,000, and more preferably 500 to 2,500. &lt;Other components&gt; The sensitized ray or radiation sensitive resin composition of the present invention may contain a dye. Preferred are oily dyes and basic dyes. In order to increase the acid production efficiency of exposure, the sensitized ray or radiation absorbing resin composition of the present invention may further contain a sensitizer. The dissolution accelerating compound which can be used in the developer of the present invention is a low molecular weight compound having 2 or -71 to 201107879 more phenolic hydroxyl groups or 1 or more carboxyl groups and having a molecular weight of 1,000 or less. When the compound has a carboxyl group, it is preferably an alicyclic or aliphatic compound. The phenol compound having a molecular weight of 1,000 or less is disclosed, for example, in JP-A-4-1 2293 8 , JP-A-2 - 2 8 5 3 1 Patent, US Patent No. 4,916,210, and European Patent No. 2 〗 9,294. The compound having a proton-accepting functional group disclosed in JP-A-2006-208781 and JP-A-2007-286574 is also preferably used in the composition of the present invention. &lt;Pattern forming method&gt; The photosensitive ray or radiation sensitive resin composition of the present invention is coated on a support (e.g., a substrate) and forms a photoresist film. The thickness of the photoresist film is preferably from 〇2 to 0.1 μm. The method of coating on the substrate is preferably spin coating, and the number of revolutions is preferably 1, Q00 to 3,000 rpm. It applies a sensitized ray or a radiation-sensitive resin composition to a substrate such as tantalum or cerium oxide for use in manufacturing a precision integrated circuit device by a suitable coating method (for example, a spin coater, an applicator, or the like). Coating). The coated substrate is then dried to form a photoresist film. It can be coated with a known anti-reflection film in advance. The photoresist film is typically exposed to a mask (preferably by electron beam (EB), X-ray or EUV radiation), preferably baked (heated), and then developed. This gives a good pattern. The developing procedure was as follows using an alkali developer. As the photoresist composition, an alkali developer can be used, for example, an alkaline aqueous solution such as an inorganic base (for example, oxyhydrogen-72-201107879 sodium, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, first grade) Amine (such as ethylamine, n-propylamine, etc.), secondary amine (for example, di-n-butylamine, etc.), tertiary amine (such as triethylamine, methyl di), alcohol amine (such as dimethylethanolamine, triethanolamine, etc.) ), (for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc.) or a ring such as pyrrole, piperidine, etc.). Further, an alkali concentration of an appropriate amount of the alcohol and the surfactant added to the above alkali developer is usually from 0.1 to 20% by mass. The pH of the alkaline developer is usually from 10.0 to 15.0. [Examples] The present invention is further described in detail with reference to the examples, but the present invention. Synthesis Example 1 Synthesis of polymer (P-I) (1) Synthesis of 4-phenylstyrenesulfonate triphenylsulfonium salt Triphenylphosphonium b salt (50 g) was dissolved in 65 ml of methylate to 30 g of 4 A mixed liquid of styrenesulfonic acid Na salt and 65 ml of a milliliter of ion-exchanged water was added dropwise to the above solution solution, and ion-exchanged water and chloroform were added to carry out extraction and washing. After concentration, the precipitated solid was slurried in hexane/ethyl acetate and passed over 48 g of 4-phenylsulfonic acid triphenylsulfonium salt. (2) Synthesis of polymer (P-1) 1-methoxy-2-propanol (10 ml) in aqueous ammonia, etc. in a nitrogen stream, such as a quaternary ammonium salt such as diethylamine ethylamine ( The alkali developer is not restricted to alcohol. In the chamber, with 130. The organic layer is filtered to obtain -73-201107879. It will contain 3.0 g (25 mmol) of 4-hydroxystyrene, 1.2 g ( 10 millimolar) 4-methylstyrene, 6.4 grams (45 millimolar) of butyl methacrylate, 1.1 grams (2-5 millimoles) of 4-styrenesulfonic acid triphenylsulfonium salt 1.2 g (5.2 mmol) of 2,2'-azobisisobutyric acid dimethyl vinegar (V-601, manufactured by Wako Pure Chemical Industries), and 20 ml of 1-methoxy-2-propanol The mixed solution was dropwise added to the above liquid over 5 hours. After the completion of the dropwise addition, the reaction solution was further stirred at 80 ° C for 3 hours. After the reaction solution was cooled, the solution was reprecipitated with a large amount of hexane/ethyl acetate and vacuum dried. Further, 7.0 g of the resin (P -1) of the present invention was obtained. The 1H-NMR of the obtained resin was observed to infer the peak caused by the OH group of 4-hydroxystyrene at around 0.9 ppm, at 2.3 ppm. A near-inference from the peak caused by the methyl group of 4-methylstyrene, the peak caused by the third butyl group of methacrylic acid third butyl acrylate near 1.4 ppm, and the inferiority of 4-styrene sulfonate near 7.8 ppm. The peak of the phenyl group of the cationic portion of the triphenylsulfonium salt, thus confirming the structure of the resin (P-1). The composition ratio of the resin is calculated from the ratio of the area of these peaks (the resin (P-1) is shown from the left side) The order of the repeating units in the structural formula is 35/15/45/5). The weight average molecular weight measured by GPC (carrier: N-methyl-2-pyrrolidone (NMP)) (Mw: poly Methyl benzene: 4,500, and Mw/Mn: 1.7. Synthesis Example 2 Synthesis of polymer (P-2) (1) 3,4,4-trifluoro-4-thioindole methacrylate Synthesis of Butyl Triphenylsulfonium Salt Triphenylphosphonium b salt (50 g) was dissolved in 65 ml of methanol. In the chamber -74-201107879, 39 g of 1,1,2-trifluoro-4-hydroxy- 1. A lithium salt of butanesulfonate (synthesized according to the method described in Solid State Ionics, 1999, 123, 233), a mixed liquid of 65 ml of methanol, and 130 ml of ion-exchanged water, and stirred into the above solution. Ion exchange water and chloroform were added to carry out extraction and washing. After concentrating the organic layer, the precipitated solid was slurried in hexane/ethyl acetate and filtered to give 31 g (40%) of methacrylic acid 3,4. 4-Trifluoro-4-thiodecyl butyl triphenyl sulfonium salt. (2) Synthesis of polymer (P-2) 1-methoxy-2-propanol (10 ml) in a nitrogen stream Heat at 80 °C. Will contain 3.0 grams (25 millimoles) of 4-hydroxystyrene, 1.3 grams (9.7 millimoles) of 4-methylstyrene, 6.4 grams (45 millimoles) of butyl methacrylate, 1.3 g (2.4 mmol) of 3,4,4-trifluoro- 4-thiodecyl butyl triphenyl sulfonium salt, 1.2 g (5.2 mmol) of 2,2'-azobispyridinium A mixed solution of dimethyl ester (V-601, manufactured by Wako Pure Chemical Industries) and 20 ml of 1-methoxy-2-propanol was added dropwise to the above liquid over 5 hours with stirring. After the end of the dropwise addition, the reaction solution was further stirred at 80 ° C for 3 hours. After the reaction solution was cooled, the solution was reprecipitated with a large amount of hexane/ethyl acetate and vacuum dried to obtain 6.6 g of the resin (P-2) of the present invention. The 1H-NMR of the obtained resin was observed to infer that the peak caused by the OH group of 4-hydroxystyrene was around 9.0 ppm, and the peak caused by the methoxy group of 4-methyl group basic ethylene was inferred around 3.7 ppm. The vicinity of 1.4 ppm is inferred from the peak caused by the tert-butyl group of the third butyl methacrylate, and the vicinity of 7.8 ppm is inferred from the 3,4,4-trifluoro-4-thiodecyl butyl triphenyl sulfonium salt. The phenyl group of the cationic moiety caused a peak, thus confirming the structure of the resin (P-2). The composition ratio of the resin was calculated from the area ratio of the peaks of -75 to 201107879 (the order of the repeating units in the structural formula of the resin (P-2) from the left side was 34/1 6/44/6). The weight average molecular weight measured by GPC (carrier: N-methyl-2-pyrrolidone (NMP)) (1^1: polystyrene, etc.) is ^^: 4,700, and ^^/^[ 11: 1.75. Synthesis Example 3 Synthesis of polymer (P-3) 1-methoxy-2-propanol (17.5 ml) was heated at 80 °C in a nitrogen stream. Will contain 10.3 grams (85.4 millimoles) of 4-hydroxystyrene, 8.0 grams (38.2 millimoles) of 2-cyclohexyl-2-propyl methacrylate, 1.7 grams (3.8 millimoles) of 4- Methyl styrenesulfonate triphenylsulfonium salt, 5.9 g (25.5 mmol) of dimethyl 2,2'-azobisisobutyrate (V-601, manufactured by Wako Pure Chemica Co., Ltd.), and 70 A mixed solution of 1 part of 1-methoxy-2-propanol was added dropwise to the above liquid over 4 hours with stirring. After the end of the dropwise addition, the reaction solution was further stirred at 80 ° C for 2 hours. After the reaction solution was cooled, the solution was reprecipitated with a large amount of hexane/ethyl acetate and dried under vacuum to give 17.1 g of the resin (P-3) of the present invention. The 1H-NMR of the obtained resin was observed to infer the peak caused by the OH group of 4-hydroxystyrene around 9.0 ppm, and to infer the cation of the triphenylsulfonium salt of 4-methylstyrenesulfonate near 7.8 ppm. Part of the phenyl caused by the peak. In addition, it was observed that the peaks caused by the methylene and methine groups of 4-hydroxystyrene and triphenylsulfonium 4-styrenesulfonate were inferred from 0.0 to 2.0 ppm, and the inference was observed from 2-methacrylic acid. The peak caused by cyclohexyl-2-propyl ester confirmed the structure of the resin (P-3). The composition ratio of the resin was calculated from the area ratio of these peaks (from the left side, -76-201107879 shows that the order of the repeating units in the structural formula of the resin (P-3) is 60/37/3). The weight average molecular weight measured by GPC was Mw: 5,000, and Mw/Mn: 1 · 6 其他 Other resins were synthesized in the same manner. Examples 1 to 3 and Comparative Examples 1 to 5 &lt;Photoresist Evaluation (EB)&gt; The compositions shown in Table 1 below were dissolved in the mixed solvent shown in Table 1, and the solid content concentration was 5.0% by mass. Solution. The solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm, and a positive resist solution was obtained. The prepared positive resist solution was uniformly coated on a crucible substrate treated with hexamethyldiazane by a spin coater, and the substrate was heated on a hot plate at 110 ° C for 90 seconds, and formed into a thick layer. 1 〇〇 nano light resist film. The photoresist film was irradiated with an electron beam by an electron beam irradiation apparatus (HL750, acceleration voltage: 50 KeV, manufactured by Hitachi Ltd.). Immediately after the irradiation, the photoresist film was baked on a hot plate at 130 ° C for 90 seconds. Then, the photoresist film was developed at 23 ° C with a concentration of 2.38 mass% of tetramethylammonium hydroxide aqueous solution for 60 seconds, washed with pure water for 30 seconds, and dried to form a line and gap pattern. The resulting pattern was evaluated by the following method. [Sensitivity] The cross-sectional form of the obtained pattern was observed with a scanning electron microscope (S-9220, manufactured by Hitachi Limited). Take the minimum exposure dose for the resolution of the 100 nm line (line and gap: 1 /1) as the sensitivity. [Resolution] The resolution of the exposure amount of the above sensitivity (the minimum line width of the analysis line and the gap can be -77-201107879, respectively) is taken as the resolution. [Line Edge Thickness (LER)] About 30 points in the longitudinal direction of 50 micrometers of the 100 nm line pattern in the display of the above sensitivity, with a scanning electron microscope (S-9220 'Hitachi, Ltd.) Measure the distance from the original baseline at the edge, and measure the standard deviation and calculate 3 σ. [Pattern form] The scanning electron microscope (S-4300, manufactured by Hitachi Limited) was used to observe the cross-sectional form of the 100 nm line pattern in which the above-mentioned sensitivity is displayed, and the three sections of the rectangle, the micro-tip and the tip are implemented. Evaluation. [Degassing] The degree of change in the film thickness (Z) at the time of the minimum irradiation energy of the 1 〇〇 nanowire (line and gap: 1 Π) is evaluated. Z = {[(film thickness before exposure) - (film thickness after exposure)] / (film thickness before exposure) 10 0 (%) After this exposure, the film thickness indicates the film thickness just after exposure 'and is entering P EB And the film thickness before the alkali development procedure. The smaller the 値, the better the performance. -78- 201107879

Hi 1 1 1 1 1 1 Degassing (Z) os wi Os r- ΓΛ Bu CO fn LER (Nano) 〇wi 〇\ 对·—— 〇 inch · Os — 〇\ — 对 · Pattern form rectangular rectangular rectangular rectangle Rectangular Rectangular Resolution (Nano) U-ί v〇Ό § VO Sensitivity (μϋ/οιη2) m CN CO (N 00 Bu «η rn cs Organic Solvent (Mixed Ratio) 4 S1/S2 (40/60) S1 /S6 j (80/20) ; S1/S5 (40/60) S1/S2 (40/60) S1/S2 ! (40/60) S1/S2 (40/60) S1/S2 (40/60) Surfactant <concentration**3 W-1 (0.05) W-1 (0.05) W-1 (0.05) W-2 (0.05) WO (0.05) W-1 (0.05) W-1 (0.05) CO mm Lesson Destroy m Destroy the acid generator (concentration) 3 Tang 壊 destroy m 堞 堞 & NE NE NE NE NE NE NE NE NE NE NE NE NE NE NE NE NE NE NE N N N N N N N N N N N N N N N N N N N N N N N N N [35/15/45/5] &lt;4,500, 1.7&gt; (99.95) P-1 [35/15/45/5] &lt;4,500, 1.7&gt; (99.95) P-2 [34/16/44 /6] &lt;4,700, 1.75&gt; (99.95) P-3 [60/37/3] &lt;5,000, 1.6&gt; (99.95) P-4 [36/14/45/5] &lt;5,000, 1.75 &gt; (99.95) P-12 [36/14/46/4] &lt;4,7〇〇, 1.73&gt; (99.95) ?A9 [35/15/47/3] &lt;4,800, 1.86&gt; (99.95) Instance number instance 1 Instance 2 Instance 3 Instance 4 Instance 5 Instance 6 Instance 7 _ec__ 201107879 1 1 1 1 i &lt; 1 Degassing (Z) &lt;N ΓΟ in «η — 对 · κη CO rn LER (Nice) cn rt* p 00 Inch Ο S wS ON ττ — o in — Pattern rectangle rectangle Rectangular rectangle: Rectangular i Rectangular rectangle Resolution (Nano) S V-) \n »nv〇in \n Ό Ό Sensitivity (μΟ/οιη2)! V&quot;&gt; 00 wn Os 〇\〇00 \ό Bu inch&lt;N (N «η 00 r*^ Organic solvent (mixing ratio)*4 S1/S2 (40/60) S1/S2 (60/40) S1/S2 (40/60) S1/S2 (40/60) S1/S2 (40/60) S1/S2 (40/60) S1/ S2 (40/60) S1/S2 (40/60) rn sis % bile W1 (0.05) Wl (0.05) Wl (0.05) Wl (0.05) Wl (0.05) Wl (0.05) Wl (0.05) W-2 (0.05) ro Gan 1 sound ^ ^ g| m 堞 destroy m destroy 璀 destroy 知acid generator (concentration) *3 destroy m destroy m destroy m destroy &lt; Ν ^ 匡 1 瞾汩 4 乸葙 silver s鹚sr Destroy the devastating class to destroy 癍 s_ V P-21 [47.5/46.5/6] &lt;4,500, 1.90&gt; (99.95) P-21 [47.5/46.5/6] &lt;4, 700,1.66&gt; (99.95) P-21 [47.5/46.5/6] &lt;4,500, 1.90&gt; (99.95) P-29 [48/47/5] &lt;4,500, 1.80&gt; (99.95) P- 30 [50/45/5] &lt;4,500, 1.80&gt; (99.95) P-35 [30/18/47/5] &lt;4.700, 1.66&gt; (99.95) P-44 [35/15/45/ 5] &lt;4,500, 1.91&gt; (99.95) P-48 P7/13/45/5] &lt;4,300, I.65&gt; 『99,95) Instance number instance 8 Instance 9 Instance 10 Instance 11 Instance 12 Instance 13 Example 14 Example 15 •08- 201107879 a 1 1 1 1 1 1 1 Degassing (Z) VT5 ui Ο ro ΓΛ 00 — LER (nano) ι〇iri Ο wi 00 — (N vj pattern rectangle rectangular rectangle Rectangular Rectangular Rectangular Resolution (Nano) v〇§ s Ό S Ό Sensitivity, (pC/cm2) (N oo rn 00 cn &lt;N 00 (N 00 Bu Os Organic Solvent (Mixed Ratio)*4 S2/ S3 (60/40) | i S1/S2 (40/60) S1/S2 (40/60) S2/S4 (60/40) S1/S2 (40/60) S1/S2 (40/60) 1 1 S1/S2 (40/60) S1/S2 (50/50) fp sis ^_ W-3 (0.05) Wl (0.05) Wl (0.05) Wl (0.05) Wl (0.05) Wl (0.05) Wl (0.05) Wl (0.05) ro Destroy m 壊TPI (0.3) ! TPI (0.3) Destroy TBA H (0-5) Conventional acid generator (concentration)*3 m Luhan mm PAG-1 i(1) Destroy &lt;N Μ ^ ϋ ^ fe! sr m P-44 [0/50/45/5] &lt;;4,300,1.65&gt; (25) P-48 [0/50/45/5] &lt;4,300, 1,65&gt; (25) PR-1 [70/30] &lt;19,000, 1.14&gt; (15) Mm PR-2 [70/30] &lt;20,000, 1.15&gt; (33) Destroy &lt;Ν £| r |ΐ|δ 靼 chain s Parrot 1 P-59 [35/15/46/4] &lt;4,300 , l,65&gt; (99.95) ! P-4 [50/0/44/6] &lt;5,000, 1.75&gt; (74.95) P-4 [52/0/42/6] &lt;5,000, 1.75&gt; (74.95) P-2 [29/26/40/5] &lt;4,500, 1.65&gt; (84.95) P-2 [34/16/44/6] &lt;4,500, 1.65&gt; (99.65) P-2 [34/16/44/6] ! &lt;4,500, 1.65&gt; 1 (98.65) P-4 [36/14/45/5] &lt;5,000, 1.75&gt; (66.95) P-4 [36/14 /45/5] &lt;5,000, 1.75&gt; (97.45) Instance Number Instance 16 Instance 17 Instance 18 Instance 19 Instance 20 Instance 21 Instance 22 Instance 23 201107879 1 1 1 1 1 1 1 Degassing (Z) (N (N LER (wire): ? TT VO inch ' ^ri case form rectangular rectangle rectangle [ rectangle 1 I rectangle i rectangle rectangle rectangle resolution (nano) sv〇§ s〇§ sensitivity (μΟ/ Ιιη2) i 26.5 CS CN (N (N (N o (N Os organic solvent (mixing ratio)*4 S1/S2 (50/50) S1/S2 (50/50) S1/S2 (50/50) S1/ S2 (50/50) S1/S2 (50/50) S1/S2 (50/50) S1/S2 (50/50) S1/S2 (50/50) Surfactant (concentration)*3 Wl (0.05) Wl (0.05) Wl (0.05) Wl (0.05) Wl (0,05) Wl (0.05) Wl (0.05) Wl (0.05) Alkaline (concentration)*3 TBAH (0.5) TBAH (0.3) TBAH (0.3 ) TBAH (0-3) TBAH (0.3) TBAH (0.3) TBAH (0.3) TBAH (0.3) Conventional antacid (concentration) 3 PAG-1 (2) m destroy m destroy 堞 resin 2 [composition ratio Γ 1 &lt;Mw, Mw/Mn&gt;*2 (concentration)*3 destroy m destroy m destroy 墀1 rs 靼 chain: s骢V P-44 [35.5/14.5/44/6] &lt;4,500, 1.91&gt; ( 97.45) P-22 [45/12/37/6] &lt;4,600, 1.85&gt; (99.65) P-29 [50/46/4] &lt;5,100, 1.89&gt; (99.65) P-40 [46/ 11/37/6] &lt;4,750, 1.81&gt; (99.65) P-55 [45/10/37/8] &lt;6,200, 1.85&gt; (99.65) P-61 [51/10/33/6] &lt;4,500, 1.91&gt; (99.65) P-62 [52/10/32/6] &lt;5,000, 1.86&gt; (99.65) P-66 [55/10/29/6] &lt;4,850, 1.83&gt ; (99.65) instance number instance 24 i instance 25 instance 26 Example 27 Example 28 Example 29 Example 30 Example 31 -CNOO- 201107879

Hi i 1 1 1 Cannot form a 100 nm L/S pattern 1 1 Cannot form a 100 nm L/S pattern Degassing (Z) 00 — Inch »〇so x&gt; v〇〇«η 〇WO 00 LER (Nemi &lt;N 0 — 0 wi (N wS 1 Ό &lt;Ν *-Η (N d pattern rectangle rectangle _1 rectangular rectangle 1 tip cone resolution (nano) S Ό Ό 1 s 00 sensitivity ( μΟ/αη2) cn (N »r&gt; (N &lt;N ri rs 1 00 (Ν' (Ν VO organic solvent (mixing ratio)*4 S1/S6 (70/30) S1/S2 (40/60) , _1 S1/S6 (70/30) S1/S6 (60/40) S1/S2 (40/60) S1/S2 (40/60) S1/S2 (40/60) S1/S2 (40/60) rp Sis w ϋ Wl (0.05) Wl (0.05) 1 Destroy Wl (0.05) W-1 (0.05) I Wl (0.05) Wl (0.05) Wl (0.05) ro V—/ TBAH (0.3) TBAH (0.3) 1 m堞堞1 ΤΡΙ (1.5) Soil m rn p Jing ^ @ marriage j gauge m Destroy 堞 PAG-1 (8) PAG-1 (8) Destroy m CN ~ Mildew A 癍 chain S flap 5g|^ 1 堞mm 堞揉 PR -3 pO/30] &lt;21,000, 1.85&gt; (49.95) 堞 (N 5P 孽 1 ^ V P-72 [40/20/30/10] &lt;5,250, 1.79&gt; (99.65) JQ § II茗v〇(N w *&gt; *Q P-1 P5/15/45/5] &lt;4,500, 1.7&gt; (10 0) P-1 [35/15/45/5] &lt;4,500, 1.7&gt; (100) PR-1 [70/30] &lt;19,000, 1.14&gt; (91.95) PR-1 [70/30] &lt;19,000, U4&gt; (90.45) PR-1 [70/30] &lt;19,000, 1.14&gt; (50) PR-4 [17/50/30/3] &lt;38,500, 2.55&gt; (99.95) Example Number example 32 Example 33 1 Example 34 Example 35 Comparative example 1 Comparative example 2 Ratio _ 3 Comparative example 4 • eoo_ 201107879 a 1 Degassing (Z) m od LER (nano) » 〇 pattern form rectangular resolution (nano) «η ν〇 sensitivity (μΟ/οιη2) rn (Ν Organic solvent (mixing ratio)*4 ν〇CO 5Γ* | ls ^ ^ V—/ Wl (0.05) fp ^ λρ ^ Sw/ m Conventional antacid (concentration) *3 buried (N two! r sgi^l^ 璐 chain S骢V m ^ C 5Γ —荽ia SS ugly|鲥v · P-1 [35/15/45/5] &lt;4,500, 1.7&gt; (99.95) Example number comparison example 5 = -if Afr.z -I-US 3El-WM -Γ

Is ..f%SN¥#i : ε* 201107879 Comparative Examples 1 and 4 cannot form a pattern of 100 nm lines (line and risk) It is apparent from Table 1 that the sensitized ray or radiation sensitive resin composition of the present invention It can simultaneously satisfy high sensitivity, high resolution, good pattern form, good line edge roughness, and degassing reduction. The materials used in the examples and comparative examples are shown below (other resins, conventional acid generators, and alkaline groups). The structure of the compound).

The surfactants and solvents used in the examples and comparative examples are shown below. W-1 : M eg af ac F 1 7 6 (D ai ni ρ ρ ο η I nk an d C hemica 1 s I nc . Manufactured) W-2 · Megafac R〇8 (manufactured by Dainippon Ink and Chemicals Inc.) W-3: polyoxyalkylene polymer (矽 surfactant, manufactured by Shin-Etsu Chemical Co., Ltd.) -85- 201107879 S1: propylene glycol monomethyl ether acetate (PGMEA, bp: 146 °c 52: propylene glycol monomethyl ether (PGME, bp: 120 ° C) 53 : methyl lactate (b.p_: 145 ° C) 54 : 5 -methyl-2-hexanone (bp ·: 145 ° C) 55 : propylene glycol monoethyl ether (bp·: 130-131 ° C) 56 : cyclohexanone (bp: 157 ° C) Example 3 6 to 3 8 &lt;Photoresist evaluation (EUV)&gt; The components shown in Table 2 below were dissolved. The solvent was mixed as shown in Table 2 and a solution having a solid content concentration of 5.0% by mass was prepared. The solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm, and a positive resist solution was obtained. The symbols in Table 2 are the same as in Table 1. The prepared positive resist solution was uniformly coated on a crucible substrate treated with hexamethyldioxane by a spin coater, and the substrate was heated on a hot plate at 120 ° C for 90 seconds, and formed. A photoresist film with a thickness of 100 nm. The photoresist film was irradiated with an EUV exposure apparatus (wavelength: 13 nm). Immediately after the irradiation, the photoresist film was baked on a hot plate at 130 ° for 90 seconds. Then, the photoresist film was developed at 23 ° C with a concentration of 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 60 seconds, washed with pure water for 30 seconds, and dried to form a line and gap pattern (line and gap: 1 /1 ). The resulting pattern was evaluated by the method shown below. [Sensitivity] The cross-sectional form of the obtained pattern was observed with a scanning electron microscope (S-9220, manufactured by Hitachi Limited). Take the analytical 丨〇 〇 nanowire (line and gap: 1 / 1) minimum exposure dose as sensitivity. -86- 201107879 [Pattern form] Observed by scanning electron microscopy (S-4 3 00, manufactured by Hitachi, Limited), the cross-sectional form of the 100 nm pattern is displayed in the above-mentioned sensitivity, and the rectangle and the microtip are implemented. Three-stage evaluation of cones and tips. -87- 201107879 眯 block bear is-N^_ Anw: (N漱 pattern form rectangle rectangle 1 rectangle sensitivity (μΟ / οιη2) 25.7 26.8 1 &lt;N organic solvent (mixing ratio) 4 S1/S2 (40/60 S1/S2 (40/60) S1/S2 (40/60) Surfactant (concentration)*3 W-3 (0.05) W-1 (0.05) W-1 (0.05) Basic compound (concentration "3璀壊 Destroy the acid generator (concentration) 3 堞 destroy CN e, | r &lt; N ^ ^ ^ § 5 ugly | 鞑 r r 壊 NE NE NE NE NE NE NE NE NE _ _ _ _ _ _ _ _ P-4 [36/14/44/6] &lt;5,000, 1.75&gt; (99.95) P-11 [35/15/45/5] &lt;4,700,1.67&gt; (99.95) P-30 [50/ 45/5] &lt;4,500,1.80&gt; (99.95) instance number instance 36 instance 37 instance 38 IWM &quot;r

Is%ΪΜΝ_&lt;ϊα鲫画插 Kw:Γ 201107879 It is known from the results shown in Table 2 that the sensitized ray or radiation sensitive resin composition of the present invention can exhibit good sensitivity and form a good pattern even when exposed to EUV. . According to the present invention, it is possible to provide an ultra-precision region, particularly in electron beam, X-ray or EUV ray lithography, while satisfying high sensitivity, high resolution, good pattern form, good line edge roughness, and Degassing is reduced, and it is also suitable as a sensitized ray or a radiation-sensitive resin composition of a positive-type photoresist composition, and a pattern forming method using the composition" on March 30, 2009 and January 25, 2010 Japanese Patent Application Nos. 2009-083708 and 2010-013681 (the patent application of which is hereby incorporated by reference in its entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire [Main component symbol description] No 0 -89-

Claims (1)

201107879 VII. Patent application scope: 1. A sensitized ray or radiation sensitive resin composition comprising: (P) a resin comprising the following repeating units (A), (B) and (C); a solvent having a boiling temperature of 150 ° C or lower, (A) a repeating unit containing a group which decomposes and forms an acid upon irradiation with actinic rays or radiation, (B) a substance containing an acid a repeating unit which decomposes and forms a group of a carboxylic acid, and (C) a repeating unit containing a carbon-carbon unsaturated bond. 2. The photosensitive ray or radiation sensitive resin composition of claim 1, wherein the repeating unit (B) is a repeating unit represented by the following formula (I), and the repeating unit (C) is represented by the following formula (π) Representation of the repeating unit: Wherein each RQ1, RQ2 and rG3 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a _ atom, a cyano group, or an alkoxycarbonyl group, and R()3 may represent an alkylene group and bond L or Q form 5_ or 6_membered ring; L represents a single bond or a divalent bond, provided that the bond represents a trivalent bond when the R bond forms a 5- or 6-membered ring; I represents an alkyl group: -90 - 201107879 Each of r2 and r3 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R2 and R3 may be bonded to each other to form a ring, provided that R2 and R3 are different when they represent a hydrogen atom: and Q represents The basis of a carbon-carbon unsaturated bond. 3. The sensitized ray or radiation sensitive resin composition of claim 1, wherein the composition of the repeating unit (B) and the repeating unit (C) in the resin (P) (mole) satisfies the repeating unit (B) S repeats the relationship of the unit (C). 4. The photosensitive ray or radiation sensitive resin composition of claim 1, wherein the resin (P) further contains (D) a species which has a function of alkali developer to decompose and increase a dissolution rate in the alkali developer The repeating unit of the base, and its system is represented by the following formula: (All): Rb〇 Wherein Rb〇 represents a hydrogen atom, a halogen atom or an alkyl group; and Ab represents a single bond, an alkylene group, a divalent linkage group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether bond, an ester bond, a carbonyl group, or a combination thereof The divalent linkage: and V represent a group which decomposes due to the action of the alkali developer and increases the rate of dissolution in the alkali developer. 5 · For example, the photosensitive ray or radiation-sensitive resin group of the second paragraph of the patent application is -91-201107879, wherein Q in the formula (II) is a group containing an aromatic ring. 6. The sensitized ray or radiation sensitive resin composition of claim 5, wherein Q in the formula (Π) is a benzene ring-containing group. 7. The photosensitive ray or radiation sensitive resin composition of claim 1, wherein the resin (P) contains a repeating unit derived from hydroxystyrene or a derivative thereof as a repeating unit (C). 8. The photosensitive ray or radiation sensitive resin composition according to the ninth aspect of the invention, wherein the repeating unit (A) has a structure in which an acid anion is generated at a side bond of the resin when irradiated with actinic rays or radiation. 9. The photosensitive ray or radiation sensitive resin composition of claim 1, wherein the solvent having a boiling temperature of 150 ° C or lower contains 65 mass % or more based on the total amount of the solvent. 1 0. The photosensitive ray or radiation sensitive resin composition of claim 1, wherein the solvent having a boiling temperature of 150 ° C or lower contains 7 5 % by mass or more based on the total amount of the solvent The amount. 1 1 · A photosensitive ray or radiation sensitive resin composition as claimed in claim 1 wherein the boiling temperature is 15 (TC or lower solvent based on the total amount of the solvent is 9 0 - 92 · 201107879% by mass Or a larger amount of the photosensitive ray or radiation sensitive resin composition according to any one of claims 1 to 11, wherein the resin (P) consists only of the repeating units (A) to (c) Or consisting only of repeating units (A) to (D), and all repeating units (C) are repeating units represented by the following formula (II-1): Q (1~1) wherein Q represents a group containing a carbon-carbon unsaturated bond. The photosensitive ray or radiation sensitive resin composition according to any one of claims 1 to 11, wherein the ratio of the repeating unit having a ring structure in the main chain in the resin (P) is 30 mol% or more. small. The photosensitive ray or radiation sensitive resin composition according to any one of claims 1 to 11, wherein the resin (P) does not contain a repeating unit having a ring structure in the main chain. The photosensitive ray or radiation sensitive resin composition according to any one of claims 1 to 11, wherein the resin (P) has a weight average molecular weight of 0 16 in the range of 1,000 to 1,000,000. The photosensitive ray or radiation sensitive resin composition according to any one of claims 1 to 11, which further comprises: an alkaline compound. The sensitized ray or radiation sensitive resin composition according to any one of claims 1 to 11, which is exposed by electron beam, X-ray or EUV ray. i. A photoresist film formed by the composition of a sensitized ray or a radiation sensitive resin according to any one of claims 1 to 11. A pattern forming method comprising: exposing and developing a photoresist film as disclosed in claim 18. -94- 201107879 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 J\\\ V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: